3-Hydr-oxy-1,2,3,9-tetra-hydro-pyrrolo[2,1-b]quinazolin-4-ium chloride dihydrate: (+)-vasicinol hydro-chloride dihydrate from Peganum harmala L.

The title compound, C(11)H(13)N(2)O(+)·Cl(-)·2H(2)O, the dihydrate of (+)-vasicinol hydro-chloride, is a pyrrolidinoquinazoline alkaloid. It was isolated from the ethyl acetate fraction of the leaves of Peganum harmala L. The pyrrolidine ring has an envelope conformation with the C atom at position 2 acting as the flap and the C atom at position 3, carrying the hydroxyl substituent, has an S configuration. The absolute configuration was determined as a result of the anomalous scattering of the Cl atom. In the crystal structure, mol-ecules stack along the a axis, connected to one another via inter-molecular O-H⋯Cl and N-H⋯Cl hydrogen bonds, forming approximately triangular-shaped R(2) (1)(7) rings, and O-H⋯Cl and O-H⋯O hydrogen bonds, forming penta-gonal-shaped R(5) (4)(10) rings. The overall effect is a ribbon-like arrangement running parallel to the a axis.

Related literature

For the isolation (+)-vasicinol and the crystal structure analysis of (+)-vasicinol hydro­bromide, see: Joshi et al. (1996 ▶). For general background on pyrrolidino-quinazoline alkaloids and their structures, see: Szulzewsky et al. (1976 ▶): Openshaw (1953 ▶); Bailey (1986 ▶); Rizk (1986 ▶); Tashkhodzhaev et al. (1995 ▶); Turgunov et al. (1995 ▶). For a study on the anti-Leishmaniasis activity of (+)-vasicinol hydro­chloride dihydrate, see: Misra et al. (2008 ▶). For further related literature on natural products, see: Hilal & Youngken (1983 ▶); Mirzakhmedov et al. (1975 ▶). For hydrogen-bond motifs, see: Bernstein et al. (1995 ▶). For puckering parameters, see: Cremer & Pople (1975 ▶).

Experimental

Crystal data

C11H13N2O+·Cl−·2H2O

M = 260.72

Orthorhombic,

a = 7.0386 (6) Å

b = 9.5752 (10) Å

c = 18.4041 (18) Å

V = 1240.4 (2) Å3

Z = 4

Mo Kα radiation

μ = 0.31 mm−1

T = 173 (2) K

0.42 × 0.19 × 0.11 mm

Data collection

Stoe IPDS diffractometer

Absorption correction: none

8680 measured reflections

2422 independent reflections

1834 reflections with I > 2σ(I)

R int = 0.034

Refinement

R[F 2 > 2σ(F 2)] = 0.029

wR(F 2) = 0.061

S = 0.90

2422 reflections

216 parameters

2 restraints

All H-atom parameters refined

Δρmax = 0.20 e Å−3

Δρmin = −0.14 e Å−3

Absolute structure: Flack (1983 ▶), 984 Friedel pairs

Flack parameter: 0.004 (64)

Data collection: EXPOSE in IPDS-I (Stoe & Cie, 2000 ▶); cell refinement: CELL in IPDS-I; data reduction: INTEGRATE in IPDS-I; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ORTEP-3 (Farrugia, 1997 ▶) and Mercury (Macrae et al., 2006 ▶); software used to prepare material for publication: SHELXL97.

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536809003766/lh2765sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809003766/lh2765Isup2.hkl

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

C11H13N2O+·Cl−·2H2O	F(000) = 552
Mr = 260.72	Dx = 1.396 Mg m−3
Orthorhombic, P212121	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2ac 2ab	Cell parameters from 6244 reflections
a = 7.0386 (6) Å	θ = 2.2–25.9°
b = 9.5752 (10) Å	µ = 0.31 mm−1
c = 18.4041 (18) Å	T = 173 K
V = 1240.4 (2) Å3	Rod, colourless
Z = 4	0.42 × 0.19 × 0.11 mm

Stoe IPDS diffractometer	1834 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.034
graphite	θmax = 26.1°, θmin = 2.2°
phi rotation scans	h = −8→8
8680 measured reflections	k = −11→11
2422 independent reflections	l = −22→22

Refinement on F2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.029	All H-atom parameters refined
wR(F2) = 0.061	w = 1/[σ2(Fo2) + (0.033P)2] where P = (Fo2 + 2Fc2)/3
S = 0.90	(Δ/σ)max < 0.001
2422 reflections	Δρmax = 0.20 e Å−3
216 parameters	Δρmin = −0.14 e Å−3
2 restraints	Absolute structure: Flack (1983), 984 Friedel pairs
Primary atom site location: structure-invariant direct methods	Flack parameter: 0.004 (64)

Geometry. Bond distances, angles etc. have been calculated using the rounded fractional coordinates. All su's are estimated from the variances of the (full) variance-covariance matrix. The cell e.s.d.'s are taken into account in the estimation of distances, angles and torsion angles

Refinement. Refinement of F2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The threshold expression of F2 > σ(F2) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F2 are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

	x	y	z	Uiso*/Ueq
O1	0.3510 (2)	0.15059 (15)	0.24928 (8)	0.0409 (5)
N9	0.2235 (3)	0.16767 (15)	0.09484 (8)	0.0249 (5)
N10	0.2348 (2)	0.40126 (14)	0.12323 (8)	0.0246 (5)
C1	0.2373 (4)	0.4955 (2)	0.18629 (12)	0.0348 (8)
C2	0.2861 (4)	0.3982 (2)	0.24882 (11)	0.0348 (7)
C3	0.2264 (4)	0.2536 (2)	0.22362 (10)	0.0280 (7)
C4	0.2242 (3)	0.0847 (2)	−0.02920 (11)	0.0310 (7)
C5	0.2242 (3)	0.1121 (3)	−0.10295 (10)	0.0373 (7)
C6	0.2232 (4)	0.2484 (3)	−0.12768 (11)	0.0398 (8)
C7	0.2228 (3)	0.3570 (2)	−0.07828 (10)	0.0339 (7)
C8	0.2231 (4)	0.45209 (19)	0.04834 (10)	0.0287 (7)
C11	0.2303 (3)	0.27062 (18)	0.14208 (9)	0.0223 (6)
C12	0.2237 (3)	0.33226 (19)	−0.00429 (9)	0.0253 (6)
C13	0.2242 (3)	0.19435 (18)	0.01937 (9)	0.0227 (6)
O1W	0.4964 (3)	0.7633 (3)	0.06429 (11)	0.0639 (8)
O2W	0.1191 (3)	0.2477 (2)	0.42346 (11)	0.0598 (8)
Cl1	0.80565 (8)	0.38150 (5)	0.32092 (3)	0.0358 (2)
H1A	0.329 (3)	0.563 (2)	0.1789 (12)	0.033 (6)*
H1B	0.113 (4)	0.540 (2)	0.1877 (14)	0.049 (7)*
H1O	0.298 (4)	0.071 (2)	0.2333 (13)	0.0610*
H2A	0.225 (4)	0.422 (2)	0.2921 (12)	0.038 (6)*
H2B	0.431 (3)	0.395 (2)	0.2595 (11)	0.040 (6)*
H3	0.095 (3)	0.231 (2)	0.2387 (11)	0.036 (6)*
H4	0.233 (3)	−0.012 (2)	−0.0084 (10)	0.034 (6)*
H5	0.222 (4)	0.034 (2)	−0.1392 (12)	0.053 (7)*
H6	0.224 (3)	0.266 (2)	−0.1810 (13)	0.047 (6)*
H7	0.217 (4)	0.454 (2)	−0.0961 (12)	0.051 (7)*
H8A	0.108 (3)	0.502 (2)	0.0441 (11)	0.029 (6)*
H8B	0.331 (3)	0.517 (2)	0.0407 (11)	0.033 (6)*
H9N	0.211 (4)	0.0872 (17)	0.1102 (11)	0.0370*
H1WA	0.432 (5)	0.792 (4)	0.099 (2)	0.0960*
H1WB	0.603 (5)	0.764 (4)	0.077 (2)	0.0960*
H2WA	0.033 (5)	0.282 (4)	0.3988 (19)	0.0900*
H2WB	0.081 (5)	0.245 (4)	0.4695 (18)	0.0900*

	U11	U22	U33	U12	U13	U23
O1	0.0538 (11)	0.0371 (9)	0.0319 (8)	0.0022 (7)	−0.0108 (7)	0.0022 (7)
N9	0.0323 (11)	0.0191 (7)	0.0233 (8)	−0.0015 (8)	−0.0018 (8)	0.0007 (7)
N10	0.0296 (11)	0.0206 (8)	0.0235 (7)	0.0004 (8)	−0.0027 (7)	0.0010 (6)
C1	0.0445 (17)	0.0241 (10)	0.0357 (11)	−0.0014 (10)	0.0015 (12)	−0.0078 (9)
C2	0.0439 (15)	0.0338 (10)	0.0268 (10)	−0.0057 (12)	0.0001 (11)	−0.0084 (9)
C3	0.0337 (16)	0.0272 (10)	0.0230 (10)	−0.0018 (10)	0.0003 (9)	0.0000 (8)
C4	0.0307 (14)	0.0319 (11)	0.0305 (10)	0.0038 (9)	−0.0018 (10)	−0.0054 (8)
C5	0.0312 (14)	0.0536 (12)	0.0272 (10)	0.0024 (13)	−0.0031 (9)	−0.0119 (11)
C6	0.0360 (15)	0.0600 (14)	0.0234 (10)	0.0003 (13)	−0.0011 (11)	0.0050 (10)
C7	0.0318 (13)	0.0429 (13)	0.0270 (10)	0.0017 (11)	−0.0002 (9)	0.0090 (9)
C8	0.0317 (14)	0.0253 (10)	0.0292 (11)	−0.0001 (11)	−0.0030 (10)	0.0075 (8)
C11	0.0194 (13)	0.0225 (9)	0.0249 (9)	0.0014 (8)	0.0003 (8)	−0.0017 (8)
C12	0.0182 (12)	0.0323 (9)	0.0253 (9)	0.0002 (9)	−0.0014 (9)	0.0027 (8)
C13	0.0199 (12)	0.0281 (9)	0.0200 (9)	−0.0006 (8)	−0.0001 (8)	0.0004 (7)
O1W	0.0428 (12)	0.1035 (16)	0.0453 (11)	0.0043 (12)	0.0030 (9)	−0.0184 (11)
O2W	0.0432 (13)	0.0885 (15)	0.0477 (11)	0.0093 (11)	0.0014 (9)	0.0226 (11)
Cl1	0.0414 (3)	0.0279 (2)	0.0380 (3)	0.0034 (2)	0.0001 (3)	−0.0046 (2)

O1—C3	1.402 (3)	C5—C6	1.382 (4)
O1—H1O	0.90 (2)	C6—C7	1.381 (3)
O1W—H1WB	0.79 (4)	C7—C12	1.382 (2)
O1W—H1WA	0.83 (4)	C8—C12	1.502 (3)
O2W—H2WA	0.83 (4)	C12—C13	1.391 (2)
O2W—H2WB	0.89 (3)	C1—H1B	0.97 (3)
N9—C13	1.412 (2)	C1—H1A	0.92 (2)
N9—C11	1.315 (2)	C2—H2A	0.93 (2)
N10—C11	1.299 (2)	C2—H2B	1.04 (2)
N10—C8	1.464 (2)	C3—H3	0.99 (2)
N10—C1	1.470 (3)	C4—H4	1.004 (19)
N9—H9N	0.825 (17)	C5—H5	1.00 (2)
C1—C2	1.520 (3)	C6—H6	1.00 (2)
C2—C3	1.519 (3)	C7—H7	0.99 (2)
C3—C11	1.510 (2)	C8—H8A	0.94 (2)
C4—C5	1.382 (3)	C8—H8B	0.99 (2)
C4—C13	1.379 (3)
C3—O1—H1O	103.1 (16)	C4—C13—C12	121.34 (16)
H1WA—O1W—H1WB	107 (4)	N10—C1—H1A	108.8 (14)
H2WA—O2W—H2WB	108 (3)	C2—C1—H1B	116.8 (15)
C11—N9—C13	120.96 (15)	N10—C1—H1B	106.2 (14)
C1—N10—C11	112.38 (15)	C2—C1—H1A	112.5 (13)
C1—N10—C8	122.67 (14)	H1A—C1—H1B	109.0 (18)
C8—N10—C11	124.78 (15)	C1—C2—H2B	112.5 (11)
C13—N9—H9N	120.4 (14)	C3—C2—H2A	110.8 (13)
C11—N9—H9N	118.5 (14)	H2A—C2—H2B	107 (2)
N10—C1—C2	102.95 (15)	C3—C2—H2B	107.6 (11)
C1—C2—C3	105.36 (17)	C1—C2—H2A	113.1 (13)
O1—C3—C2	111.4 (2)	O1—C3—H3	109.7 (12)
O1—C3—C11	113.54 (17)	C11—C3—H3	108.6 (12)
C2—C3—C11	101.54 (15)	C2—C3—H3	111.9 (11)
C5—C4—C13	119.47 (19)	C13—C4—H4	117.1 (11)
C4—C5—C6	120.2 (2)	C5—C4—H4	123.3 (11)
C5—C6—C7	119.61 (19)	C4—C5—H5	120.8 (12)
C6—C7—C12	121.29 (19)	C6—C5—H5	119.0 (12)
N10—C8—C12	110.68 (14)	C7—C6—H6	121.4 (11)
N9—C11—C3	125.13 (16)	C5—C6—H6	119.0 (11)
N10—C11—C3	111.72 (15)	C12—C7—H7	119.3 (13)
N9—C11—N10	123.11 (16)	C6—C7—H7	119.4 (13)
C8—C12—C13	121.58 (15)	N10—C8—H8B	107.4 (12)
C7—C12—C8	120.30 (16)	N10—C8—H8A	107.1 (12)
C7—C12—C13	118.12 (16)	H8A—C8—H8B	109.2 (17)
N9—C13—C4	119.99 (16)	C12—C8—H8A	109.6 (12)
N9—C13—C12	118.67 (15)	C12—C8—H8B	112.7 (12)
C13—N9—C11—N10	1.2 (3)	O1—C3—C11—N10	−135.24 (18)
C13—N9—C11—C3	178.7 (2)	C2—C3—C11—N9	166.7 (2)
C11—N9—C13—C4	177.6 (2)	C2—C3—C11—N10	−15.5 (3)
C11—N9—C13—C12	−2.8 (3)	C13—C4—C5—C6	−0.3 (3)
C8—N10—C1—C2	−170.1 (2)	C5—C4—C13—N9	179.8 (2)
C11—N10—C1—C2	14.5 (3)	C5—C4—C13—C12	0.2 (3)
C1—N10—C8—C12	179.9 (2)	C4—C5—C6—C7	0.2 (4)
C11—N10—C8—C12	−5.3 (3)	C5—C6—C7—C12	0.1 (4)
C1—N10—C11—N9	178.6 (2)	C6—C7—C12—C8	−180.0 (2)
C1—N10—C11—C3	0.7 (3)	C6—C7—C12—C13	−0.3 (3)
C8—N10—C11—N9	3.3 (3)	N10—C8—C12—C7	−176.89 (19)
C8—N10—C11—C3	−174.5 (2)	N10—C8—C12—C13	3.4 (3)
N10—C1—C2—C3	−23.3 (3)	C7—C12—C13—N9	−179.5 (2)
C1—C2—C3—O1	144.52 (19)	C7—C12—C13—C4	0.1 (3)
C1—C2—C3—C11	23.3 (3)	C8—C12—C13—N9	0.2 (3)
O1—C3—C11—N9	47.0 (3)	C8—C12—C13—C4	179.8 (2)

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1O···Cl1i	0.90 (2)	2.20 (2)	3.086 (2)	171 (2)
N9—H9N···Cl1i	0.83 (2)	2.35 (2)	3.155 (2)	167 (2)
O1W—H1WA···Cl1ii	0.83 (4)	2.39 (4)	3.204 (2)	167 (3)
O1W—H1WB···O2Wii	0.79 (4)	1.96 (4)	2.720 (3)	162 (4)
O2W—H2WA···Cl1iii	0.83 (4)	2.35 (4)	3.173 (2)	175 (3)
O2W—H2WB···O1Wiv	0.89 (3)	1.83 (3)	2.718 (3)	179 (5)

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1—H1O⋯Cl1i	0.90 (2)	2.20 (2)	3.086 (2)	171 (2)
N9—H9N⋯Cl1i	0.83 (2)	2.35 (2)	3.155 (2)	167 (2)
O1W—H1WA⋯Cl1ii	0.83 (4)	2.39 (4)	3.204 (2)	167 (3)
O1W—H1WB⋯O2Wii	0.79 (4)	1.96 (4)	2.720 (3)	162 (4)
O2W—H2WA⋯Cl1iii	0.83 (4)	2.35 (4)	3.173 (2)	175 (3)
O2W—H2WB⋯O1Wiv	0.89 (3)	1.83 (3)	2.718 (3)	179 (5)

Symmetry codes: (i) ; (ii) ; (iii) ; (iv) .